Monoazo acid dyestuffs



Patented Sept, 1313, I545 Arthur ti e itan-ht and William. ElliotStephen, Blaehiey, England, assignors to Impen-all ilii'eifie'alIndustries Limited, a. corporatron oi Great Britain Narrowing.Application September 17, 1942, Se-

No. 458,732. In Great Britain October is,

Claims. ('01. 260-199) 3 will The present relates to the manufacture ofnew monom acid dyestuffs and to their application to colouring of animalfibres.

to the invention we make the dye= stull's by fiazotising an amine of thei I formula a hich R stands for a benzene nucleus which may be furthersubstituted with simple azo dyestuff swbstituents, for example methyl,methoxy or sulphonic acid groups, X stands for a monochloroor'inonobromo-alkyl radical having not more than three carbon atoms, Ystands for hydrogen or an alkyl (C1 to C6), aralkyl, cycloalkyl,

ako fiyalky1 or aryl radical, and the primary amiho group in the meta orpara position to the K--CONY- group, and coupling the diazo compoundso-obtained with a derivative of 2- amino- -5naphthol-'l-sulphonic acid(J -acid) in lwhftiia one H of the NHz group is replaced by was acylgroup -COM, where M is an aliphatic l'iydrocarbon radical with not morethan 6 car- :bon atoms, and the other H may be replaced by an alkyl oraryl group.

Also according to the invention we use the dyestuiTs in colouring animalfibres, silk.

' The dyestuffs dye wool from an acid dyebath, various shades of orangebeing obtainable; the dyeings are characterised 'very good fastness tosevere washing and milling, and good fastness to light. 7

As examples of t'iiazo components which can be employed according to theinvention, we mentic-n: l-ah'lino-LIN-ethyl-omega-chloroacetanilide,41-amino-i-N-isopropyl-omega-chloroacetanilide,l-amino-l-N-n-butyl-omega-chloroacetanilide, i-amino-Z-N-ethy1-omega-chloroacetetoluidide, i-amino -2-N-ethyl-omega-bromopropiontolui- 'dide, i l B-aminO-Omega chloroacetanilide 4 sulphonic acid,2-a'mino-4N-ethyl-omega-chloroacet-toluidide, 4amino-Z-N-ethyl-a-bromobutyryl-toluidine,. '4ainino-2-N-ethyl-u-bromopropion-to1uidide, '4 a 1hino-2- N ethyl omegachloropropiontoluiiiide, V N l-amino-1-N-ethy1-omegachloropropionanilide, 4-amino-1-N-ethyl-omega=bromopropionaniliqe,

e. a, wool and i-amino-l N-sec-butyl omegachloroacetanilide,a-amino-omega chloroacetanilide 3 sulphonic t f4=amino-2-N-ethyl-omegachloroacetanisidide, 4-amino-1-N-n-butyl-omega-chloroacetanilide-Z-sulphonic acid, 4-amino-1-N-ethyl omega bromoacetanilide,Jr-amino-1-N-benzyl-omega-chloro-acetanilide, 4-amino-1-N-cyclohexylomega chloroa'cetanilide,5-amino-2-N-cyclohexybomega-chloroacet-toluidide,3-amino-leN-benzyl-omega-chloroacetanililde,4-.amino-2-N-benzy1@omega-chloroacet-toluidide,

"l-amino-l-N-phenyl-omegaohloroacetanilide,

4-amino-1-N-cyclohexyl omega ohloropropiom anilide, j a 4-amino-1-N-cyclohexylaomega bromopropiom anilide, v j ll-amino-l-Necyclohexyl-az-bi ofnolfiropiohahilide, 4-amin01-N-cyolohexyl-ornega bromo-acetani= lideand l 4-.ami'no-2-N-benzyl-omega-chloro-actanisidide (obtainable by methodsdescribed in British Pat ent No. 544,409 or our U. S. PatentN0.'2,346,492)

acetanilide (obtainable by acetylating N-fi-ethoxyethylaniline,nitrating, removing the acetyl group by hydrolysis,'causing theresulting l nitro-l-N-fi-ethoxyethylaniline to react with chloroacetylchloride in boiling toluene and reducing the-nitro-l-N-fl-ethoxyethyhomega chloroa'cetanilide thus obtained.

As examples of coupling components which can be employed according'totheinvention, we menyuan 2-acetylamin0-, 2-propionylamino-,Z-n-butyrylam'ino 2-N-methyland iethyl-N acetylamino-5' naphthol7-sulphonie acids and 2 -N- phenyl N-acetylamino-5-naphtho1 7 -sulphonicacid. 2-propionylamino and 2-n-butyry1amino- 5-naphthol7 sulphonic acidsare obtained by reacting aqueous solutions containing one molecularproportion of the sodium salt of 2-amino-5- naphthol-i-sulphonic acidwith rather more than one molecular proportion of propionic andn-butyrio. anhydrides respectively, until no diazotisable prim ry minecan. bedetected, and salting out the acylatedproductsf, 2-N t ylrN- l tym nQ- l 'p h le'7-sulphonic acid can be .ob- W 1??? y'addi ig to aqueoussolution ofone molecular proportion of the soduim salt of 2-N-ethylamino--naphthol-'T-sulphonic acid rather more than one molecularproportion of acetic anhydride and stirring the mixture for some timeuntil the reaction product no longer couples with diazotisedp-nitroaniline in mineral acid medium to give a violet colouration. Theresulting liquor containing the reaction product can be used fordyestufi preparations if desired.

The following examples, in which the parts are by weight, illustrate butdo not limit the invention.

7 Example 1 21.25 parts of ii-amino-l-N-ethyl-omega-chloroacetanilideare dissolved in a mixture of. .300 parts of water and 25 parts of 36%hydrochloric acid and then 6.9 parts of sodiumm'trite areadded. Thediazo compound 'so-obtained, after cooling to 5-10 C. is added to astirred andcooled mixture of 305 parts of the sodium salt of 2-acetylamino-5-naphthol 7 sulphonic acid, 80 parts of sodium chloride,350-parts oiiwater and suflicient sodium carbonate to keep the couplingmixture alkaline to litmus. When coupling-is complete moresodiumchloride isadded, the mixture stirred forseveral hours andthe dyestufifiltered off and dried.

Itis orangeebrownin colour and dissolvesin water with a reddish-orangecolour. It dyeswool from a dyebath containing sulphuricacidand.

Glaubers saltin reddish-orange. shades, thedyeingshaving very goodfastness to. severe-washing, millingand light.

Example 2 ,salt in reddish-orange shades, the dyeings having 22.6 partsof .4-amino-2-N-ethyl omega-ch1oroacet toluidide are dissolved in a .mixture of 350 partsot water and parts .of 36%. hydrochloric acid and tothe solution at 5 10 C. there are adde 6- r p q md it tees lutiq of thedia'zo compound so-obtained is addedwith s ir ing to a coQEdm Xiur 0 .3P S 0 the sodium salt of 2-acetylamino-5-naphthol-7 sulphonic acid in400 parts of waterto which 80 parts of sodium chloride have beenaddedhandw suificient sodium carbonate or sodium bicarbonate to. keepthe coupling medium alkaline. The new dyestuff so-obtained is isolatedand dried.

:It dyeswool imbright reddish-orange shades when applied. from .adyebath containing sul-.

.5 'The diazo solution, after cooling to 10 C., is

phuricacid and Glaubers salt, the dyeings having "very good fastness toseverewashing, milling and i light.

If the ;above coupling is carried out in-the presence of excess sodiumacetate instead of sodium. carbonate or sodium bicarbonate a-;dyeflstufiisobtained yielding on-wool somewhat yellower shades of bright reddishorange.

7 Example 3 .dium carbonate. r dyestufi is isolated and dried. It isorange in dissolves in water with a reddish-orange colour. It dyes Woolfrom a dyebath containing sulphuric acid and Glaub-ers salt inreddish-orange shades, the dyeings having very good fastness to severeWashing, milling and light.

Example 4 22.6 parts of 4-amino-2-N-ethyl-omega-chloroacet-toluidide arediazotised as in Example 2. The diazo solution so-obtained is added to astirred aqueous solution at about 10 C. of 31.9 parts of the sodium saltof 2-propio-ny'lamino-5- naphthol-Y-sulphonic acid containing excess so-When coupling is complete the ing,-milling and light.

Ear ampl e 5 24.05 parts of 4-amino-1N-n-butyl-omegachloro-acetanilideare dissolved in 400 parts of water and 30 parts of 36% hydrochloricacid r and to the cooled solution 6.9 parts of sodium nitrite are added.

' The solution of'the diazo compound so-obtained is-filtered, ifnecessary, and added to a cooled and stirred solution of 30.3 parts ofthe sodium salt of 2acetylamino-5-naphthOl-7-sulphonic acid containingsufllcient sodium carbonate to keep the coupling mixture alkaline tolitmus.

'The'new, dyestuff issalted out if necessary, filtered off and dried. Itdyes wool from a dyebath containing sulphuricaacid and Glaubers verygood fastness to severe Washing, milling and light.

If, in the above coupling, the sodium carbonate 0. employed is replacedby 34 parts of crystallised :sodium acetatea dyestufi is obtained whichyields on wool somewhat yellower' and brighter .shades of reddishorange, the 'dyeings having similar fastness properties.

Example '6 22.65 parts of 4-amino-1-N-ethyl-omegachloro-propionanilideare dissolved in 400 parts of water and 25 parts of 36% hydrochloricacid and then 6.9 parts of sodium nitrite are added.

gradually added to a stirred solution at 10 C.-l5 C. of 30.3 parts ofsodium 2-acetylamino-5- naphthol-Y-sulphonate and 28 parts ofcrystallised sodium acetate in 400 parts of water. Stir- ;ring iscontinued until coupling is complete when the new dyestuff is filteredoff, washed with 5% aqueous sodium chloride, and dried.

It forms a scarlet powder, is soluble in water with a reddish orangecolour, and dyes wool from an acid bath inreddish orangeshades, thedyeings having good. fastness to severe Washing, milling, and light.

If instead of,4-amino-1-Neethyl-omega-chloropropionanilide there is usedthe equivalent weight of 4-amino-1-N-ethyl-omega-bromopriopionanilide adyestufi is obtained having very similar properties of shade andfa'stness.

"Example 7 24 parts of 4-amino-2'-N-ethyl-omega-chloropropiontoluidideare diazotised by the method described in' Example 2. The solution ofthe diazo compound so-obtainedisadded slowly to.a stirred solution at510 C. of 30.5 parts of sodium 2- acetylamino--naphthol-7-sulphonate and28 parts of crystallised sodium acetate in 400 parts of water. Whencoupling is complete, 40 parts of sodium chloride are added and theprecipitated dyestuff filtered on, washed with 5% sodium chloridesolution, and dried.

It forms a bright scarlet powder, soluble in water, and dyes wool from adyebath containing sulphuric acid and Glaubers salt in bright reddishorange shades, the dyeings having good fastness to severe washing,milling and light.

Example 8 28.85 parts of 4-amino-2 N benzyl omegachloroacettoluidide aredissolved in 400 parts of water containing 25 parts of 36% hydrochloricacid and the solution cooled to 5-7 C. A solution of 7.0 parts of sodiumnitrite in 50 parts of water is then added. The solution of the diazocompound so-obtained, after filtration if necessary, is gradually addedto a solution of 5 -7 C. of 30.3 parts of the sodium'salt of2'-.acetylamino- 5-naphthol-7-sulphonic acid in 400 parts of water, towhich have. been added 21 parts of anhydrous sodium carbonate and 80parts of sodium chloride. Coupling is rapid and, when complete, the newdyestuff is filtered. oh" and dried. It dyes wool from an acid bath inorange shades, the dyeings having very good fastness to severe washingand milling.

Example 9 27.45 parts of B-amino 1- N benzyl-omegachloroacetanilide arediazotised by the method of Example 8. The diazo solution so-obtained isfiltered, if necessary, and added gradually at 5-7 C. to a stirredsolution at 57 C. of 30.3 parts of the sodium salt of 2-acetylamino-5-naphthol-'l-sulphonic acid in 400 parts of water, to which have beenadded 21 parts of anhydrous sodium carbonate. Coupling is rapid and,when it is complete, the new dyestufi is salted out if necessary,filtered off and dried. It dyes wool from an acid bath in bright orangeshades, the dyeings having very good fastness to severe washing, millingand light.

The above couplingmay also be carried out in the presence of similarmild neutralising agents such as sodium bicarbonate or sodium acetate.

Example 10 26.65 parts of 4-amino-l-Npsrclohexyl-omegachloroacetanilideare dissolved in 400 parts of water and 25 parts of 36% hydrochloricacid and diazotised at -30 C. by the addition of a solution of 6.9 partsof sodium nitrite in 50 parts of water. The solution of the diazocompound 50- obtained, is added, after filtration if necessary, withstirring to a cooled solution of 30.3 parts of the sodium salt of2-acetylamino-5-naphthol-7- .sulphonic acid in 400 parts of water towhich have been added 21 parts of anhydrous sodium carbonate and 80parts of sodium chloride. The new dyestuff so-obtained is filtered offand dried. It dyes wool from an acid bath in reddish-orange shades, thedyeings having very good fastness to severe washing and milling, andgood iastness to light.

If instead of 30.3 parts of the sodium salt of 2-acetylamino 5 naphthol7 sulphonic acid there are employed 31.7 parts of the sodium salt of 2propionylamino-5-naphthol 7 sulphonic acid or 33.1 parts of the sodiumsalt of n-butyrylamino 5 naphthol-7-sulphonic acid, dyestufi's areobtained having similar properties.

28.05 parts of 4-amino-l-Ncyclohexyl-omegachloropropionanilide aredissolved with warming in 150 parts of water and 35 parts of 36%hydrochloric acid and the resulting solution then diluted with a further150 parts of water. Diazotisation is effected at 20-2'5 C. by theaddition of 7 parts of sodium nitrite. The solution of the diazocompound so-obtained, after filtration is necessary, is cooled to 1012C. and added grad-- ually to a similarly cooled and stirred mixture of30.3 parts of sodium 2-acetylamino-5-naphthol- 7-sulphonate, 400 partsof water and 45 parts of crystallised sodium acetate. Stirring iscontinued for about three hours after which coupling is complete. 50parts of sodium chloride are then added and the new dyestu'ifv filteredoff, washed with 5% aqueous sodium chloride and dried.

It dyes wool from a dyebath' containing sulphuric acid and Glaubers salt'in bright reddish orange shades. the dyeings having good fastnessExample 12 A solution of 25.65 parts of4-amino-1-N-pethoxyethyl-omega-chloroacetanilide in 250 parts of waterand 25 parts of 36% hydrochloric acid is diazotised by the addition of6.9 parts of sodium nitrite. The diazo solution so-obtained is addedgradually at 1015 C. to a stirred mixture of 30.3 parts of sodium2-acetylamino-5-naphthol- 7-sulphonate, 28 parts of sodium acetatecrystals and 350 parts of water. When coupling is complete 30 parts ofsodium chloride are added to precipitate the dyestuff which is thenfiltered ofi, washed with 10% aqueous sodium chloride, and

dried.

The new dyestuff forms a red powder soluble in water to an orangesolution and in concentrated sulphuric acid to a scarlet solution. Itdyes wool from an acid bath in reddish orange shades of very goodfastness to severe washing and milling and good fastness to light. 7 I

Example 13 26 parts of l-amino-l-N-phenyl-omega chloroacetanilide aredissolvedin 400 parts of water and 25 parts of 36% hydrochloric acid anddiazotised by the addition of 6.9 parts of sodium 'nitrite. The diazosolution, after filtration if necessary, is added to a stirred solutionat 5-10 C. of 30.3 parts of sodium2-acetyl-amino-5-naphthol-7-sulphonate in 400 parts of water to which 30parts of crystallised sodium acetate have been added. Stirring iscontinued for half an hour after which coupling is complete. The newdyestuff is precipitated by the addition of parts of sodium chloride,filtered off, washed with 10% aqueous sodium chloride and dried. Itforms a reddish brown powder which dissolved in water to give a reddishorange solution and in concentrated sulphuric acid to give a redsolution.

The new dyestuff dyes wool from an acid dyebath in dull, very reddishorange shades, the dyeings having very good fastness to severe washingand milling.

The invention is further illustrated by the examples listed in thefollowing table;

Ex- V. Acid binding Shade given by ample D1azo component Couplingcomponent agent used in the dycstufi on No. coupling wool 144-amino-2-N-ethyl omega chloroacettolui- 2-N-acetyl-N-ethylamino-5-naphthol-7- Sodium carbonate. D ull yellowishdide. l sulphonic acid. sea 4-gnino-2-Nethyl a bromopropiontolui-Z-acetylamino-fi-naphthol-7-sulphonic acid do Reddish orange.

1 e. 16 i 'izmng-N ethyl-omegwbromo propiontdo do Do. 1 v 173-amino-omega-chloroacetanilide-4-tulphonic s--do Sodium acetate.Orange.

aci 18 4-a1nino-Z-N-ei:heyl-omega-chloroacettoluid-2-N-acjetyl-N-pheny1a1i1ino-5-naphthol-7- Sodium carbonate. V e r y r ed dis h ide. sulphonic acid. orange. 194-amino-Y-N-n-butyl-omega-chloroacetan- 2 N n butyrylamino 5 naphthol 7Sodium acetate, Orange.

1 ilide, s sulphonic acid. 20 4 aI Il1 ilO l N ethyl omega -chloroacet-;do Sodium carbonate- Do. am 1 e. 1 21. l. 4 amino; 1 N soc butyl omegachloro- 2 acetylamino 5 naphthol 7 'sulphonic Sodium acetate Do.

acetanilide. acid. 22 4 ani gio 1 e N ethyl omega-bromoacet- ,.do .4 doReddish orange.

am 1 c. v V v 23 4 amino omega chloroacetanilide 3 sul- ..do do Scarlet.phonic acid. g I 24 4 amino l N cyclohexyl omega bromo- 2 N acetylN-ethylamino-fi naphtholdo' Reddish orange.

acetanilide'. 7-sulphonic acid. v U H I V v v 25:4...1; 4 amino l Ncyclohexyl omega chloro- 2 N acctyi N-phenylamino-fi-nophthol- Sodiumcarbonate. Dull yery reddish acetanilide. 7.-sulphonic ac orange. 1 26d0 2 N acetyl N methylamino 5 naph- Sodium acetate. Reddish orange rthol-7-sulphonic acid. 27 4 amino 1 N cyclohexyl omega chloro- 2propionyl amino 5 naphthol 7 sul do Do'.

propionanilide. phonic acid. I i 4 v 28 4 amigo 2 N benzylomegaohloroacet- 2 acgtylamino 5 naphth'ol 7 sulphoni'c Sodiumcarbonate. Scarlet.

an1s1 1 e. ac1 29.; 5 amino 2 N cyclohexyl omega chlorodo Sodiumbicarbon- Reddish orange.

acettoluidide. me.

We claim: 3. The monazo dye which in the form of its 1. A monazo dyewhich in the form of its acid is represented by the formula 0 acid isrepresented by the formula,

Y A Z I 2115 0H 7 4. The monaZo dye which in the form of its H acidisrepresented by the formula 40 E038 *N( 3-CH;

wherein X is a mono-halogeno-alkyl group hav- H irig not more than 3carbons in which halogen is one of the group consisting of chlorine andbromine; Y is one of a group consisting of hydrogen, alkyl having 1 to 6carbons, lower alkoxyalkyl, c'ylohexyl, benzyl and phenyl; --Rr-*'NH2 isan aryl nucleus of the group consisting of aniline and toluino which issubstituted I 2. A monazo dye in accordance with claim 1 in which thediazo component is unsulfonate'd.

o111,o-( ?Nc,m OH

. V O Q 5. The monazo dye which in the form of its acid is representedby the formula ARTHUR HOWARD KNIGHT. WILLIAM ELLIOT STEPHEN.

